WO1999041011A1 - Tube a reaction metallique a recouvrement catalytique - Google Patents

Tube a reaction metallique a recouvrement catalytique Download PDF

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Publication number
WO1999041011A1
WO1999041011A1 PCT/EP1999/000901 EP9900901W WO9941011A1 WO 1999041011 A1 WO1999041011 A1 WO 1999041011A1 EP 9900901 W EP9900901 W EP 9900901W WO 9941011 A1 WO9941011 A1 WO 9941011A1
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WO
WIPO (PCT)
Prior art keywords
tube
reaction
reactor
tubes
multimetal oxide
Prior art date
Application number
PCT/EP1999/000901
Other languages
German (de)
English (en)
Inventor
Signe Unverricht
Heiko Arnold
Andreas Tenten
Otto Machhammer
Peter Zehner
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19805719A external-priority patent/DE19805719A1/de
Priority claimed from DE1998139782 external-priority patent/DE19839782A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU30275/99A priority Critical patent/AU3027599A/en
Publication of WO1999041011A1 publication Critical patent/WO1999041011A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00281—Individual reactor vessels
    • B01J2219/00286—Reactor vessels with top and bottom openings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00306—Reactor vessels in a multiple arrangement
    • B01J2219/00313—Reactor vessels in a multiple arrangement the reactor vessels being formed by arrays of wells in blocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00511—Walls of reactor vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00513—Essentially linear supports
    • B01J2219/0052—Essentially linear supports in the shape of elongated tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B01J2219/00612—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports the surface being inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B01J2219/00614—Delimitation of the attachment areas
    • B01J2219/00621—Delimitation of the attachment areas by physical means, e.g. trenches, raised areas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B01J2219/00632—Introduction of reactive groups to the surface
    • B01J2219/00637—Introduction of reactive groups to the surface by coating it with another layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00659—Two-dimensional arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/00745—Inorganic compounds
    • B01J2219/00747—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B30/00—Methods of screening libraries
    • C40B30/08—Methods of screening libraries by measuring catalytic activity
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/18—Libraries containing only inorganic compounds or inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries

Definitions

  • the invention relates to a metallic reaction tube with a catalytic coating, preferably on the inner wall of the tube, tube bundle reactors with coated reaction tubes, a coating method and a use of the reaction tube or the tube bundle reactor in catalytic gas phase oxidation for the production of (meth) acrolein and / or (meth) acrylic acid.
  • WO 97/25146 discloses a catalytically active coating which consists of a layered composite with a metallic base body, for example the inside of a reaction tube, an adhesion promoter and a catalytically active cover layer made of, in particular, oxide-ceramic catalyst material.
  • a catalytically active coating which consists of a layered composite with a metallic base body, for example the inside of a reaction tube, an adhesion promoter and a catalytically active cover layer made of, in particular, oxide-ceramic catalyst material.
  • a large-scale heterogeneously catalyzed reaction is the catalytic gas phase oxidation of C, -C 6 -alkanes, C 2 -C 6 alkenes, C r C 6 alkanols and / or - alkanals and / or precursors thereof for the preparation of (meth) acrolein and / or (meth) acrylic acid.
  • These reactions are highly exothermic, which is why, due to the large number of possible parallel or subsequent reactions, it is necessary for a selective reaction to control the course of the reaction temperature.
  • the reaction tubes are surrounded by a heat transfer medium, for example a molten salt.
  • This object is to be achieved in a simple manner, by means of a suitable design of the reaction tubes, without special requirements on the temperature profile and flow guidance of the heat exchange medium circuit.
  • the object is achieved according to the invention by providing a metallic reaction tube with a catalytic coating, the coating containing a multimetal oxide mass which is applied directly to the reaction tube.
  • a coating process for the production of the corresponding metallic reaction tubes or tube bundle reactors is also to be made available.
  • multimetal oxide composition denotes oxidic mixtures which contain two or more, preferably three or more chemical elements, generally not more than 50 different chemical elements in a proportion of more than 1% by weight.
  • transition metal elements molybdenum and bismuth are always contained in the multi-metal oxide materials used according to the invention. Usually they are
  • Multimetal oxide materials are not simple physical mixtures of oxides of the elemental constituents, but heterogeneous mixtures of complex poly compounds of these elements.
  • the multimetal oxide compositions used according to the invention generally contain molybdenum, calculated as MoO 3 , in a proportion of 20 to 90% by weight, preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight.
  • the catalytic coating containing the multimetal oxide mass is applied directly to the reaction tube, i.e. without intermediate supports or adhesive intermediate layers.
  • the inner wall of the metallic reaction tube is preferably provided with the catalytic coating.
  • the catalytic coating according to the invention preferably has a layer thickness of 10 to 1000 ⁇ m, preferably 20 to 500 ⁇ m, particularly preferably 50 to 350 ⁇ m.
  • the invention relates to tube-bundle reactors with metallic reaction tubes which, in accordance with the above statements, are provided with a catalytic coating which contains a multimetal oxide composition applied directly to the reaction tubes, preferably to the inner wall of the tube.
  • the reaction tubes of the tube bundle reactor can have any cross section, which is, however, generally round, in particular circular.
  • the inner tube diameter is preferably 0.2 to 70 mm, in particular 10 to 50 mm, particularly preferably 15 to 30 mm.
  • the tube bundle reactor can generally contain up to 50,000 reaction tubes, preferably 50 to 40,000, particularly preferably 500 to 30,000 reaction tubes.
  • the tube length is generally 0.1 to 10 m, preferably 0.3 to 8 m, particularly preferably 0.5 to 6 m.
  • a bed of multimetal oxide full or shell catalysts into the reaction tubes, preferably in their entirety, in particular with a fill level of 5 to 90%, preferably 10 to 70%, especially 20 to 50% of the total Reactor tube length.
  • the catalyst bed is preferably installed in the area on the gas outlet side.
  • a tube reactor with fully or partially coated reaction tubes is followed by a second reactor, in particular a tube reactor, which is equipped with a bed of multimetal full oxide or shell catalysts is provided.
  • a second reactor in particular a tube reactor, which is equipped with a bed of multimetal full oxide or shell catalysts is provided.
  • This arrangement of two reactors connected in series offers the advantage that, depending on the degree of progress of the reaction, it is possible to work under different, particularly adapted process conditions.
  • the tubes of which carry the catalytic coating according to the invention at temperatures which are generally around 20 to 100 ° C. higher than the conventional gas phase oxidation to (meth) acrolein and / or ( Meth) acrylic acid, typically from 200 to 450 ° C, are worked.
  • the tubes of which carry the catalytic coating according to the invention at temperatures which are generally around 20 to 100 ° C. higher than the conventional gas phase oxidation to (meth) acrolein and / or ( Meth) acrylic acid, typically from 200 to
  • the coating method according to the invention comprises the following steps
  • a liquid starting mixture is produced in the form of a
  • the liquid mixtures generally contain a liquid chemical component, which is used as a solvent, emulsifying agent or Dispersing aid is used for the other components of the mixture.
  • a liquid chemical component which is used as a solvent, emulsifying agent or Dispersing aid is used for the other components of the mixture.
  • water is preferably used and / or one or more organic compounds whose boiling point or sublimation temperature at normal pressure is> 100 ° C., preferably> 150 ° C.
  • the organic proportion of the liquid chemical to be used according to the invention is preferably
  • the liquid mixtures contain one or more, preferably 2 or more, preferably 3 or more chemical elements, but generally not more than 50 different chemical elements, each with an amount of more than 1% by weight. % are included.
  • the chemical elements in the mixtures are preferably present in very intimate mixing, e.g. in the form of a mixture of various miscible solutions, intimate emulsions with small droplet size and / or preferably as a suspension (dispersion), which the chemical elements in question generally in the form of a fine-particle precipitation, e.g. in the form of a mixed chemical fall.
  • sols and gels has also proven particularly useful, in particular those which contain the chemical elements in question in a largely homogeneous distribution, and preferably those which have an adhesive and flow behavior which is favorable for the subsequent coating.
  • the starting compounds for the selected chemical elements are in principle the elements themselves, preferably in finely divided form, and in addition all compounds which contain the selected chemical elements in a suitable manner, such as oxides,
  • Hydroxides oxide hydroxides, inorganic salts, preferably nitrates, carbonates,
  • Starting compounds can be used in solid form, in the form of solutions, emulsions and / or in the form of suspensions.
  • the liquid mixture can contain other compounds that Affect adhesive properties and the flow behavior of the liquid mixture on the surface to be coated.
  • Organic compounds such as ethylene glycol or glycerol as described in DE-A 44 42 346 or maleic acid copolymers, for example, and inorganic compounds such as SiO 2 , silicon organic compounds or siloxanes are to be mentioned here.
  • the mixtures used can additionally contain an inorganic and / or organic binder or a binder system which stabilizes the mixture used.
  • Binder or binder systems which contain metal salts, metal oxides, metal oxide hydroxides, metal oxide hydroxide phosphates and / or eutectic compounds melting at the operating temperature of the catalyst.
  • the mixture can also be adjusted in a defined pH range by adding acids and / or bases. In many cases pH-neutral suspensions are used.
  • the mixture can advantageously be adjusted to a pH between 5 and 9, preferably between 6 and 8. Special results can be achieved with the process according to the invention if the mixture has a high solids content of up to 95% by weight, preferably 50 to 80% by weight, with a low viscosity.
  • the mixture is stirred after and generally also during production and its flowability is measured continuously, but at least at the end of production. This can e.g. by measuring the current consumption of the stirrer. With the help of this measurement, the viscosity of the suspension can e.g. can be adjusted by adding further solvents or thickeners in such a way that optimum adhesion, layer thickness and layer thickness uniformity result on the surface to be coated.
  • the coating is carried out with the manufactured ones Mixtures, preferably by means of a spraying process or by immersion, on various parts of a metallic reaction tube or the tubes of a tube bundle reactor, in particular on the tube inner walls, in a 10 to 1000 ⁇ m, preferably 20 to 500 ⁇ m, particularly preferably 50 to 350 ⁇ m thick layer.
  • the mixture can be poured into the individual tubes and spun at speeds between 200 and 1000 rpm, preferably at speeds between 300 and 800 rpm.
  • the coatings are produced on the inside of the reaction tubes by spraying on the above-mentioned liquid mixture.
  • the sprayed-on mixture material presses itself into the roughness of the surface, preventing air bubbles under the coating.
  • the mixture used can adhere completely to the sprayed inside. However, a portion of the mixture can also be discharged again by dripping, particularly if the mixture has less adhesion and / or the viscosity is low.
  • the auxiliary supports to be coated for example in the form of inner tubes, can be coated completely or only partially.
  • the respective reactor tube inlet and reactor tube outlet can be left out of the coating by a suitable device in order to prevent later sealing problems with the supply and discharge devices for the fluid to be connected.
  • a coating in which the mixture is sprayed into the preheated tube or this mixture is introduced into the preheated tube by immersion has also proven useful.
  • the metallic base body is preheated to 60 to 500.degree. C., preferably 200 to 400.degree. C. and particularly preferably 200 to 300.degree. C. before the suspension is sprayed on, and coated with the mixture described at the outset at this temperature.
  • a large part of the volatile constituents of the mixture is evaporated and a preferably 10 to 2000 ⁇ m, preferably 20 to 500 ⁇ m, particularly preferably 50 to 350 ⁇ m thick layer of the catalytically active metal oxides on the metallic base body - 10 -
  • the reaction tubes can also be coated several times in succession. Separate drying and / or calcining and / or sintering steps can be interposed between the individual coatings of a reaction tube.
  • the inner wall coating is advantageously carried out with the aid of one or more spray lances, preferably with one or more movable spray lances.
  • the spray lance is used during the spraying process e.g. drawn through the pipe to be coated with the aid of an automatic device at a defined constant or varying speed.
  • the thickness of the applied layer after drying and optionally calcination or sintering is preferably 10 to 1000 ⁇ m, particularly preferably 20 to 500 ⁇ m.
  • the adhesion of the catalytic layer can be increased by chemical, physical or mechanical pretreatment of the inner tube before coating.
  • the inner tubes can e.g. be pickled with bases or preferably with acids.
  • the inner tube is roughened by blasting with a dry blasting medium, in particular corundum or quartz sand, in order to support the adhesion.
  • detergents which have a suspension of hard particles, e.g. Corundum, in a dispersion liquid.
  • the coating previously applied is freed of the preferably aqueous solvent by drying.
  • sintering or calcination of the particles forming the coating can also take place.
  • the actual catalytically active coating is generally obtained in this process.
  • Tube bundle reactor with reaction tubes with catalytic coating Since the danger of the formation of hot spots is avoided in this method, the temperature can be higher, in particular by approximately 20 to 100 ° C.
  • a calcined catalyst of the gross composition given above was ground, then 100 g of this powder were intimately mixed with 100 g clycerin and the resulting suspension was applied by immersion to the inside of a reaction tube having the dimensions given above at room temperature. The tube was then annealed at 300 ° C for two hours. The coating process was then repeated and, after coating twice, a multimetal oxide catalyst layer (35 g of active composition) was obtained.
  • the selectivity of the reaction with respect to acrolein and acylic acid is significantly improved. Even at an increased reaction temperature (400 ° C) compared to Comparative Example 1, a higher selectivity to acrolein and acrylic acid (95.6%) compared to a selectivity of only 93.2% at a lower reaction temperature of 360 ° C is achieved. - 13 -
  • a stainless steel spiral with a wall width of 1.5 cm and a wall thickness of 2 mm for intensive gas swirling was installed and investigated in a tube coated in accordance with Example 2.
  • the improved gas mixing due to the installation of the stainless steel spiral leads to an improved selectivity of the reaction to acrolein and acrylic acid.
  • Example 3 The spiral from Example 3 was coated analogously to the coating in Example 2 with a catalyst powder / clycerol mixture by immersion (10 g active composition on the spiral coil) and tested.
  • the selectivity is significantly improved by coating the stainless steel spiral with the multimetal oxide catalyst.
  • Example 2 In a tube which was coated analogously to Example 2 (35 g of active composition on the inside of the tube), 100 g of conventional unsupported catalyst were installed in the reactor outlet in accordance with Example 1. The bed height was 30 cm.
  • the combined use of the catalyst as a coating and at the same time as a full catalyst significantly improves the selectivity compared to the conventional use of the catalyst as a full catalyst.
  • Example catalyst ReaMons selectivity to selectivity temperature acrolein and COJ% ⁇ PC] acrylic acid

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un tube à réaction métallique pourvu d'un recouvrement catalytique, ainsi qu'un réacteur à faisceaux de tubes, constitué de tubes à réaction pourvus d'un recouvrement. Ledit recouvrement contient une masse constituée de plusieurs oxydes métalliques qui est appliquée directement sur les tubes à réaction, en particulier sur la ou les parois intérieures de ces tubes. Un tel tube à réaction ou un tel réacteur à faisceaux de tubes peut en particulier être utilisé dans le procédé de production de (méth)acroléine et/ou d'acide (méth)acrylique par oxydation catalytique en phase gazeuse.
PCT/EP1999/000901 1998-02-12 1999-02-11 Tube a reaction metallique a recouvrement catalytique WO1999041011A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU30275/99A AU3027599A (en) 1998-02-12 1999-02-11 Metallic reactor tube with catalytic coating

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19805719A DE19805719A1 (de) 1998-02-12 1998-02-12 Verfahren zur kombinatorischen Herstellung und Testung von Heterogenkatalysatoren
DE19805719.9 1998-02-12
DE1998139782 DE19839782A1 (de) 1998-09-01 1998-09-01 Metallisches Reaktionsrohr mit katalytischer Beschichtung
DE19839782.8 1998-09-01

Publications (1)

Publication Number Publication Date
WO1999041011A1 true WO1999041011A1 (fr) 1999-08-19

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008009466A1 (fr) * 2006-07-21 2008-01-24 Evonik Stockhausen Gmbh Dispositif et procédé pour la préparation d'acide acrylique avec tendance réduite à l'auto-oxydation
US7799373B2 (en) * 2003-04-03 2010-09-21 Basf Se In situ recoating of catalyst beds
US10792703B2 (en) 2017-11-21 2020-10-06 New Mexico Tech University Research Park Corporation Aerosol method for coating

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3679603A (en) * 1970-01-07 1972-07-25 Artur Maximovich Garnish Catalyst for oxidation of olefins
DE2118871A1 (de) * 1971-04-19 1972-10-26 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Carbonsäuren oder deren Anhydriden
EP0040666A1 (fr) * 1980-05-23 1981-12-02 Röhm Gmbh Procédé d'oxydation et de déshydrogénation catalytique et application d'un dispositif approprié pour sa mise en oeuvre
EP0351167A1 (fr) * 1988-07-11 1990-01-17 Sumitomo Chemical Company, Limited Procédé de préparation d'acide méthacrylique
WO1992013637A1 (fr) * 1991-02-06 1992-08-20 Gastec N.V. Systemes precurseurs de catalyseurs ou de membranes; systemes de catalyseurs ou de membranes et procede de preparation desdits systemes
DE4431949A1 (de) * 1994-09-08 1995-03-16 Basf Ag Verfahren zur katalytischen Gasphasenoxidation von Acrolein zu Acrylsäure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3679603A (en) * 1970-01-07 1972-07-25 Artur Maximovich Garnish Catalyst for oxidation of olefins
DE2118871A1 (de) * 1971-04-19 1972-10-26 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Carbonsäuren oder deren Anhydriden
EP0040666A1 (fr) * 1980-05-23 1981-12-02 Röhm Gmbh Procédé d'oxydation et de déshydrogénation catalytique et application d'un dispositif approprié pour sa mise en oeuvre
EP0351167A1 (fr) * 1988-07-11 1990-01-17 Sumitomo Chemical Company, Limited Procédé de préparation d'acide méthacrylique
WO1992013637A1 (fr) * 1991-02-06 1992-08-20 Gastec N.V. Systemes precurseurs de catalyseurs ou de membranes; systemes de catalyseurs ou de membranes et procede de preparation desdits systemes
DE4431949A1 (de) * 1994-09-08 1995-03-16 Basf Ag Verfahren zur katalytischen Gasphasenoxidation von Acrolein zu Acrylsäure

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7799373B2 (en) * 2003-04-03 2010-09-21 Basf Se In situ recoating of catalyst beds
WO2008009466A1 (fr) * 2006-07-21 2008-01-24 Evonik Stockhausen Gmbh Dispositif et procédé pour la préparation d'acide acrylique avec tendance réduite à l'auto-oxydation
US10792703B2 (en) 2017-11-21 2020-10-06 New Mexico Tech University Research Park Corporation Aerosol method for coating

Also Published As

Publication number Publication date
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